Incorporation of metallated nucleosides into DNA at fixed and known locations is crucial to examination of electron transfer rates and the variation of these rates with structure, distance, and position. A new synthetic strategy has been developed for covalent attachment of ruthenium acceptor and donor complexes to duplex DNA through solid phase synthesis. Three series of metallated duplexes are proposed in which to investigate the effect of 1) donor-acceptor distance, 2) site of donor or acceptor covalent attachment, and 3) driving force on the rates of electron transfer in DNA. The rates will be measured by transient absorption spectroscopy, and distance dependence and driving force parameters will be obtained through data manipulation. The insight gained from these studies will allow determination of structural parameters of electron transfer in DNA.
|Frank, Natia L; Meade, Thomas J (2003) 5' modification of duplex DNA with a ruthenium electron donor-acceptor pair using solid-phase DNA synthesis. Inorg Chem 42:1039-44|